Textile marking composition



Patented Aug. 27,1940

UNITED STATES PATENT OFFICE terchemical Corporation, New York, N.

corporation of Ohio No Drawing. Application April 7, 1938, Serial No; 200,801

Claims.

This invention relates to textile printing, and has particular application to new and novel compositions for printing colored designs on textiles, and to the improved textiles obtained thereby. More particularly, it contemplates the printing of textiles with marking compositions comprising dispersions of pigment in vehicles consisting essentially of a mixture of ethyl cellulose and nitrocellulose. V

The conventional method of coloring textiles is to dye them in the piece, or to" print dyes in various designs on the textiles. The dye printing of textiles is an expensive operation, and

often open to serious objections due to the failure of many dyes to resist li' ght, washing, dry cleaning and other incidents of normal use. Furthermore, fine designs reproduce poorly, due to the tendency of the dye pastes to spread.

It has been proposed to print textiles by the use of pigmented compositions, formed by dispersing pigment in a variety of binders, applying the compositions in a manner similar to the printing of paper, directly to the untreated fabric. This method of textile decorating has obvious advantages over the dye printing method, since it eliminates the treatment of the fabric before and after printing, necessary in dye print! ing, permits the use of the cheaper, more lightresistant covering pigments, and gives finer prints. It also permits the use of fabrics which have slight defects, since the pigment tends to hide the defects.

Although the use of pigmented marking compositions possesses very great advantages over the conventional dyeprinting methods,'the method has had but little application, due primarily to other objectionable qualities of the pigmented coating compositions.

A principal objection to these pigmented compositions is the development of what is known in the trade jargon as handa certain objectionable stifl feel of the cloth in handling, as compared with the smooth feel of the unprinted cloth. This is due only slightly to the thickness of the coating on the individual yarn; it is probably due primarily to the bridging of the film from one yarn of the fabric to the next, whereby agglomerates of yarns are formed which give the impression on handling that the fabric is woven from coarse thread. It is therefore essential that the composition yield a discontinuous film which does not bridge the yarns of the fabric unduly.

A second principal objection is the phenomenon known as crocking, which is the tendency of the printed fabric to yield color to another fabric, or to the hand, when rubbed against it. While this phenomenon is observable with many dyestufi' prints, it is far more serious with pigmented'prints,and is one of the principal objections of the trade to pigment-printed fabrics.

A pigmented marking composition must not only meet the requirements of not crocking appreciably, and not giving a noticeable hand to the fabric, but must also meet other requirements. Adhesion to fabric, suflicient strength, flexibility and extensibility to withstand crush.- ing, crumpling and stretching of the fabric, good resistance to washing and dry cleaning agents, and the ability to withstand ironing, are all essential characteristics of a desirable print.

The combinationof all of these properties in a single vehicle is obviously difficult of attainment. Extensibility and flexibility are limited by thermoplasticity and a tendency to stick while ironing; a great many desirable film-forming ingredients may not be used because they 'do not Withstand soap or dry cleaning solvents; and most flexible films which are also strong enough to wear well have their usefulness impaired by the hand. they impart to the fabrics. The problem is further complicated by the fact that film forming binders often act entirely differently in the discontinuous films desirable in textile printing, as compared to the continuous films obtained in the ordinary printing, marking and coating of paper, textiles, wood and non-porous materials.

Attempts have been made to use nitrocellulose as a binder for textile marking compositions, but two serious difliculties have been encountered. First, nitrocellulose undergoes gradual decomposition, particularly under the influence of ultraviolet radiation. In decomposing, it gives off oxides of nitrogen which attack many pigments and ultimately destroy them. Secondly, nitrocellulose by itself is horny and gives the goods a very considerable hand because of its horny toughness. When it is treated with plasticizers in sufllcient amount to make it flexible, its binding strength is so seriously impaired that the pigment is no longer firmly bound and the prints crock seriously. Cellulose acetate has likewise not proven satisfactory, because its binding strength is not suflicient when plasticized to flexibility.

I have discovered that ethyl cellulose has many desirable properties for use as a binder for pigmented textile marking compositions, including remarkable flexibility when plasticized, a tendency to yield rather than break when overloaded, good wetting properties for most pigments and resistance to ultraviolet. But ethyl cellulose cannot be used-as a binder for most textile marking compositions because of its easy solubility in the constituents or ordinary dry cleaning fluids, such as benzol and carbon tetrachloride.

I have further discovered that the desirable properties of ethyl cellulose can be'utilized and its principal defect eliminated by combining it with nitrocellulose. When nitrocellulose and ethyl cellulose are used together, and the ratio of nitrocellulose to ethyl cellulose is not less than 1 to 3, the tendency of the latter to dissolve and soften in dry cleaning fluids is inhibited, and such combinations are insoluble in aromatic hydrocarbons, chlorinated aliphatic hydrocarbons, and aliphatic hydrocarbons. The mixtures retain the basic desirable properties of ethyl cellulose until the proportion of nitrocellulose to ethyl cellulose reaches more than 3 to 2, when the effect of the nitrocellulose becomes dominant in the combination, and unsatisfactory textile inks are obtained. In general, a proportion of 1 to l meets the requirements of textile marking binders.

These combinations of ethyl cellulose and nitrocellulose in the indicated ratios are excellent bases for lacquers intended for textile printing, possessing the desirable properties 'of straight ethyl cellulose, while at the same time yielding prints which are resistant to dry cleaning.

In making a composition in accordance with my invention, I may disperse the pigment in either the nitrocellulose or the ethyl cellulose by any known method, and combine such dispersions into lacquers in known manner. The lacquers must be properly plasticized to give the necessary flexibility, and to reduce the tendency of the unplasticized film to bridge between threads. The plasticizer must be used in amount equal to at least 50% by weight of the cellulose derivative, and more desirably should equal or exceed the cellulose derivative. In general, any of the plasticizers commonly used with nitrocellulose can be employed. Among those which I have found suitable are dibutyl phthalate, tricresyl phosphate, the toluene sulphonamide plasticizers, glycol succinate, methyl abietate, and alkyd resins.

Typical formulae embodying my invention are the following:

EXAMPLE I.-YeZZow printing paste Parts by weight Chrome yellow pigment 6 15-20 sec. nitrocellulose (wet with 30% alcohol) Ethyl cellulose (low viscosity) 5 Gelled castor oil 2 Dibutyl phthalate 10. Butyl acetate 10 Bvtanol 5 Toluene 42 Ethyl acetate 15 EXAMPLE II.-Red printing paste Parts by weight Parts by weight Phthalocyanine blue 2.0 4; sec. nitrocellulose 3.0 Ethyl cellulose (low viscosity) 7.5 Blown castor oil 4.0 Tricresyl phosphate 3.0 Butyl acetate 15.0 Butanol 5.5 Toluene 50.0 Ethyl acetate 10.0

ExAMPLs-IV.Green printing paste Parts by weight Brilliant green 3.0

sec. nitrocellulose I 4.5 Ethyl cellulose (low viscosity) Y 4.5 Gelled castor oil 4.0

Sipalin AOM (dimethyl cyclohexanyl adipate) 7.5 Butyl acetate 5.0 Butanol 5.0 Toluene 35.0 Ethyl acetate 21.5 Petrobenzol 10.0

EXAMPLE V .-Br0wn printing paste Parts by weight Iron oxide brown"; 8.0 /2 sec. nitrocellulose 5.5 Ethyl cellulose (low viscosity) 5.5 Tricresyl phosphate 12.5 See. amyl acetate 10.0 Butanol 10.0 Toluol 35.0 Ethyl acetate 13.5

While I have shown but a few examples of my invention, changes in pigment, solvent and plasticizers can obviously be made without departing from the spirit of the invention. The nitrocellulose and ethyl cellulose used may be of any desirable viscosity to produce the desired viscosity in the marking composition, although better results are obtained by using lower viscosity materials. Various textile fabrics may be printed, but care should be taken to avoid solvents for the fabric when printing on cellulose derivative fabrics; I

What I claim is:

1. A textile printing ink comprising a pigment dispersed in a vehicle comprising a solution of nitrocellulose and ethyl cellulose in organic solvents, the ratio of nitrocellulose to ethyl cellulose being between 1 to 3 and 3 to 2.

2. A textile fabric bearing markings insoluble in benzol and carbon tetrachloride, said markings comprising pigment dispersed in a binder comprising nitrocellulose and benzol soluble ethyl cellulose, the ratio of nitrocellulose to ethyl cellul0sebelngbetweenlto3and3to2.

3. A textile marking composition comprising a solution of nitrocellulose, water-insoluble ethyl cellulose and plasticizer in organic solvents, the ratio of nitrocellulose to ethyl cellulose being betweenltoaand3to2.

4. A textile iabric bearing markings insoluble in bennol and carbon tetrachloride, said markings comprising coloring matter protected by a binder 

